Gel composition and production method therefor

ABSTRACT

Provided is a production method for a gel composition including steps (1) to (3) mentioned below: step (1) of mixing at room temperature a partial degradation product of the galactose moiety of galactoxyloglucan and an aqueous solvent to obtain a mixture; step (2) of cooling or freezing the mixture obtained in step (1); and step (3) of gelling the mixture cooled or frozen in step (2) by heating to obtain a gel composition that includes the galactose-partial degradation product.

CROSS REFERENCE TO RELATED APPLICATION

This application is the U.S. National Phase Application ofPCT/JP2016/068891, filed Jun. 24, 2016, the contents of such applicationbeing incorporated by reference herein.

FIELD

The present invention relates to a gel composition and production methodtherefor.

BACKGROUND

Conventionally, galactoxyloglucan is known as a natural polysaccharide.Galactoxyloglucan includes glucose, xylose, and galactose as constituentsugars, a main chain of which has β-1,4-bonded glucose, and a side chainof which has xylose and galactose bonded to the xylose.Galactoxyloglucan itself is not usually gelled, while being gelled inthe presence of saccharide, ion, or alcohol.

Meanwhile, there has been proposed a partial degradation product of thegalactose moiety of galactoxyloglucan, which is obtained by partiallydegrading (partial degradation) to remove a galactose moietyconstituting a part of the side chain of galactoxyloglucan using refinedβ-galactosidase derived from microorganisms (hereinafter also referredto simply as “galactose-partial degradation product”) (see PatentLiteratures 1 and 2). When galactose-partial degradation product ismixed with an aqueous solvent, a mixture thereof shows a thermalbehavior having a reversed relationship with the thermal behavior of thegalactoxyloglucan. Specifically, the galactose-partial degradationproduct is gelled when heated and solated when cooled so that it shows athermal behavior in this sol/gel change is reversible. Such a thermalbehavior is called reverse thermal gelation characteristics. Thegalactose-partial degradation product is derived from naturalpolysaccharides and is not subjected to chemical modification(addition), and therefore is harmless to humans and the environment.Therefore, gel compositions produced using the galactose-partialdegradation product can be widely used in foods, cosmetics,pharmaceutical formulations and the like. There have been proposed, as aproduction method for a gel composition including a galactose-partialdegradation product of this kind, a method for producing a gelcomposition by mixing a cooled aqueous solvent with a galactose-partialdegradation product to allow the galactose-partial degradation productto dissolve in the aqueous solvent, and gelling the dissolved solutionby heating (see Patent Literatures 1 and 2).

CITATION LIST Patent Literature

Patent Literature 1: JP 118-283305

Patent Literature 2: International Publication WO97/29777

SUMMARY Technical Problem

In general, it is said that an aqueous solvent is preferably mixed withpolysaccharides in order to prevent formation of undissolved lumps atthe time of contact of the aqueous solvent with the polysaccharides, inorder to easily produce a gel composition including polysaccharides.This is because a powdery solid matter (nonhydrate product) resultingfrom nonhydrated polysaccharides remains in the produced gelcomposition, which causes deterioration in quality. Also, a long timeand much labor are needed to dissolve polysaccharides which have becomeundissolved lumps by completely hydrating deep inside thepolysaccharides.

In this regard, according to the methods of Patent Literatures 1 and 2,a method employed is that, when producing a gel composition using agalactose-partial degradation product, the galactose-partial degradationproduct is mixed with a cooled aqueous solvent to allow themselves to bedissolved. However, these methods necessitate cooling an aqueous solventfollowed by mixing of the galactose-partial degradation product, whichtakes a lot of time and labor for preparation. These methods also causeexcessive viscosity of the mixture, which may cause difficulty inhandling when it is transferred to a desirable container and is gelledby heating. Also, these methods may cause a difficulty in filling adesirable container with a sufficient amount of the mixture or cause airbubbles to be easily entrained in the mixture during preparation orfilling of a solution. Thus, it is hard to say that a gel compositioncan be easily produced by these methods of Patent Literatures 1 and 2.

In view of the above circumstances, it is an object of the presentinvention to provide a production method that is capable of easilyproducing the gel composition including a partial degradation product ofthe galactose moiety of galactoxyloglucan, and a gel compositionproduced by the production method.

Solution to Problem

In order to achieve the aforementioned object, the inventors of thesubject application have diligently studied as mentioned below. It isgenerally known that, when a polysaccharide is mixed with an aqueoussolvent, water in the aqueous solvent causes the polysaccharide to firsthydrate and swell, and when the hydration and swelling further proceeds,the polysaccharide dissolves. As a result of taking into account thisfact and the methods of Patent Literatures 1 and 2, it has been foundthat, since the methods of Patent Literatures 1 and 2 include a step ofdissolving a galactose-partial degradation product by being mixed with acooled aqueous solvent, the dissolved solution has a relatively highviscosity, which results in difficulty in handling of the dissolvedsolution. Also, as the temperature of the aqueous solvent is lowered bycooling, the time required for the galactose-partial degradation productto come into the hydration and swollen state, further the time requiredfor it to convert from the hydration and swollen state into thedissolved state are shortened. Because of this, it was found that, inthe methods of Patent Literatures 1 and 2, viscosity develops at anearly stage, and therefore, the dissolved solution must be forciblystirred with a relatively strong force in order to homogeneouslydisperse the galactose-partial degradation product in the aqueoussolvent. As a result of the diligent studies based on these findings,the inventors of the subject application have found that, by mixing theaqueous solvent and the galactose-partial degradation product at roomtemperature, the galactose-partial degradation product can be dispersedin an aqueous solvent without occurrence of undissolved lumps in amixture. Such mixing at room temperature causes the galactose-partialdegradation product to be easily brought into a state where it is almostundissolved in the aqueous solvent, which results in producing a mixturehaving a low viscosity. Further, cooling or freezing the mixture havingsuch a low viscosity causes the galactose-partial degradation product tobe easily brought into a state where it is not dissolved but is easy tohydrate and swell in a high viscous state, which results in producing amixture having a high viscosity. Further, there is no need to cool theaqueous solvent in advance, by which time and labor for it iseliminated. It has also been found that, even if a mixture with thegalactose-partial degradation product almost hydrated and swelledtherein is heated, the mixture can be gelled and hence a gel compositioncan be produced. Thus, the present invention have been achieved.

Specifically, according to the present invention, there is provided aproduction method for a gel composition, including steps (1) to (3)mentioned below:

step (1) of mixing at room temperature a partial degradation product ofthe galactose moiety of galactoxyloglucan and an aqueous solvent toobtain a mixture;

step (2) of cooling or freezing the mixture obtained in step (1); and

step (3) of gelling the mixture cooled or frozen in step (2) by heatingto obtain a gel composition that includes the galactose-partialdegradation product.

The “room temperature” herein means a temperature within a range of from15 to 35° C. “Mixing at room temperature” means mixing with the aqueoussolvent being at room temperature. The state “cooled” means a statewhere the mixture of the aqueous solvent and the galactose-partialdegradation product is not solidified by lowering the temperature, andalso means the state where liquefied portions and solidified portions(i.e., frozen portions) are both present. The state “frozen” means astate where the mixture of the aqueous solvent and the galactose-partialdegradation product is solidified by lowering the temperature.

Meanwhile, in the present description, the “dispersed” state of thegalactose-partial degradation product means a state where, while theaqueous solvent penetrates galactose-partial degradation product whichis entirely in powder form, it is present in the aqueous solvent withlittle formation of a highly viscous (adhesive) layer on the surfacelayer. The state “hydrated and swollen” means a state where thegalactose-partial degradation product which is entirely in powder formfully absorbs the aqueous solvent, and the galactose-partial degradationproduct as a whole is kept in a highly viscous state. The state“dissolved” means a state where polysaccharide molecule chains aredetached from the highly viscous surface layer and disperse from thesurface layer into the solvent. The state “undissolved lumps” means astate where the galactose-partial degradation product in powder form asa whole is lumped or such undissolved lumps are further form a group,resulting from that the galactose-partial degradation product in powderform which is in aggregated form (forming a aggregated product) comesinto contact with water, allowing only the outer layer of the aggregatedproduct having an air layer contained therein to form a highly viscousstate by the contact with water, and thereby making the aqueous solventless penetrate the inside of the aggregated product.

In step (1) of the production method for the gel composition having theabove construction, the galactose-partial degradation product and theaqueous solvent are preferably mixed at 18 to 30° C.

In step (1) of the production method for the gel composition having theabove construction, 30 to 55% of the galactose moiety is preferablydegraded in the galactose-partial degradation product.

In step (2) of the production method for the gel composition having theabove construction, the mixture obtained in step (1) is preferablycooled or frozen to −25 to 10° C.

In step (1) of the production method for the gel composition having theabove construction, 0.05 to 20 mass % of the galactose-partialdegradation product is preferably included in the mixture.

In the production method for the gel composition having the aboveconstruction, the aqueous solvent preferably includes water or saltaqueous solution.

The gel composition according to the present invention includes apartial degradation product of the galactose moiety of galactoxyloglucanobtained by the aforementioned production method for the gelcomposition.

BRIEF DESCRIPTION OF DRAWINGS

The FIGURE is a graph showing a relationship between time and viscosityafter a galactose-partial degradation product is dispersed in water atroom temperature.

DESCRIPTION OF EMBODIMENTS

Hereinafter, embodiments of a production method for a gel compositionand a gel composition produced by the production method according to thepresent invention will be described.

A production method for the gel composition of this embodiment includessteps (1) to (3) mentioned below:

step (1) of mixing at room temperature a partial degradation product ofthe galactose moiety of galactoxyloglucan and an aqueous solvent toobtain a mixture;

step (2) of cooling or freezing the mixture obtained in step (1); and

step (3) of gelling the mixture cooled or frozen in step (2) by heatingto obtain a gel composition that includes the galactose-partialdegradation product.

The partial degradation product of the galactose moiety ofgalactoxyloglucan used for the production method of this embodimentmeans a substance, which is obtained by partially dissolving to removethe galactose moiety on the side chain of galactoxyloglucan, and thepartial degradation product of the galactose moiety of galactoxyloglucanhereinafter may be abbreviated as the galactose-partial degradationproduct. Galactoxyloglucan means galactoxyloglucan (completegalactoxyloglucan) of which the galactose moiety on the side chain isnot removed by partial degradation with later-described enzymetreatment. This complete galactoxyloglucan may also be referred to asnative galactoxyloglucan.

Galactoxyloglucan is a constituent of a cell wall (a primary wall) of ahigher plant such as dicotyledon and monocotyledon, and exists as astorage polysaccharide of some plant seeds. Galactoxyloglucan includesglucose, xylose, and galactose as constituent sugars, a main chain ofwhich has β-1,4-bonded glucose, and a side chain of which has xylose andgalactose bonded to the xylose. Galactoxyloglucan itself is not usuallygelled, while being gelled in the presence of saccharide, ion, oralcohol.

Galactoxyloglucan may be galactoxyloglucan derived from any plants andobtainable from, for example, seeds of tamarind, jatoba, and nasturtium,cereal such as soybean, mung bean, kidney bean, rice, and barley, orskin of fruits such as apple. A preferable one is galactoxyloglucanderived from leguminous-plants tamarind seed because of the easiestavailability and the large content of galactoxyloglucan. A commerciallyavailable one can be employed as such galactoxyloglucan.

The galactose-partial degradation product used for the production methodof this embodiment is produced by the following production methods, forexample. Specifically, the galactoxyloglucan derived from tamarind seedis maintained at 55° C. and then adjusted to pH 6 with trisodiumcitrate, followed by addition of β-galactosidase thereto, to react at 50to 55° C. for 16 hours, while being stirred. Subsequently, after theenzyme is deactivated by heating at 95° C. for 30 minutes, the obtainedproduct is returned to room temperature, followed by addition of anequal volume of ethanol thereto, to be left standing for 1 hour.Precipitates which were obtained after being left standing are collectedby way of suction filtration and dried with a ventilation drier, andthereafter the precipitates are pulverized to thereby produce agalactose-partial degradation product.

β-galactosidase to be used may be any product derived from plants ormicroorganisms, but a preferable one is enzyme derived frommicroorganisms such as Aspergillus oryzae and Bacillus circulans, orenzyme present in a galactoxyloglucan-containing seed. A commerciallyavailable one can be employed as such a β-galactosidase.

In the enzyme reaction with this β-galactosidase, the galactose moietyon the side chain of the galactoxyloglucan is partially removed with theprogress of reaction, and when the galactose removal ratio reaches about30%, the reaction solution is rapidly thickened in viscosity and gelled.When the galactose removal ratio is in the range of 30 to 55%, thegalactose-partial degradation product has reverse thermal gelationcharacteristics, whereby it is gelled when heated and solated whencooled. The galactose-partial degradation product tends to be not gelledwith the galactose removal ratio of less than 30%, whilegalactose-partial degradation product tends to form an excessively hardgel with the removal ratio over 55% (see JP 118-283305 and InternationalPublication WO97/29777).

In consideration of this, it is preferable to use the aforementionedgalactose-partial degradation product in which 30 to 55% of a galactosemoiety is degraded. By setting the removal ratio within this range, itis possible to produce a gel composition that is not excessively hard,while allowing it to exhibit sufficient gelation characteristics byheating. This makes it easier to allow the galactose-partial degradationproduct to exhibit the reverse thermal gelation characteristics wherebyit is fully gelled when heated and fully solated when cooled in areversible manner.

The aforementioned galactose-partial degradation product in which 30 to55% of a galactose moiety is degraded is produced from galactoxyloglucanin which 30 to 55% of a galactose moiety is degraded as mentioned above.Galactoxyloglucan usually includes about 37% of a side-chain xylose andabout 17% of a side-chain galactose (see Gidley, et al., CarbohydrateResearch), 214 (1991), pp. 219-314). Therefore, it is calculated thatthe galactose-partial degradation product in which 30 to 55% of agalactose moiety is degraded includes 39 to 41% of a side-chain xyloseand 8 to 12% of a side-chain galactose. The ratio of degradation of agalactose moiety (that is, the galactose removal ratio) can becalculated by measuring an amount of galactoxyloglucan oligosaccharidesgenerated by cellulase degradation of the obtained partial degradationproduct with high performance liquid chromatography (HPLC) (aminocolumn).

In step (1) in the production method for this embodiment, thegalactose-partial degradation product and the aqueous solvent are mixedat room temperature to thereby obtain a mixture thereof. Morespecifically, a dispersion liquid (i.e., suspension liquid) as a mixturein which the galactose-partial degradation product has been dispersed inthe aqueous solvent can be obtained by mixing the galactose-partialdegradation product with the aqueous solvent at room temperature.

As mentioned above, as the temperature of the aqueous solvent is loweredby cooling, the time required for the galactose-partial degradationproduct to reach the hydration and swollen state and the time requiredfor the galactose-partial degradation product to be transformed from thehydration and swollen state into the dissolved state are shortened. Insuch a state where the time required for the galactose-partialdegradation product to reach the dissolved state is relatively short, arelatively strong stirring force is required in order to disperse thegalactose-partial degradation product in the aqueous solvent ashomogeneously as possible. That is, a relatively strong stirring forceis required in order to dissolve the galactose-partial degradationproduct in the cooled aqueous solvent as homogeneously as possible.

On the other hand, the time required for the galactose-partialdegradation product to reach the hydration and swollen state in theaqueous solvent at room temperature and the time required for thegalactose-partial degradation product to reach the dissolved state aremuch longer than those in the case of using the cooled aqueous solvent,and therefore, the galactose-partial degradation product hardlydissolves even when the stirring is performed with the same force asthat mentioned above. Accordingly, the occurrence of undissolved lumpscaused by the galactose-partial degradation product can be suppressed bymixing the galactose-partial degradation product with the aqueoussolvent at room temperature in step (1).

A gathered powder seems to occur in a dispersion liquid during mixing ofthe galactose-partial degradation product with an aqueous solvent.However, this is not an undissolved lump and therefore thegalactose-partial degradation product can be easily dispersed almostcompletely by lightly crumbling the gathering with spatula (spatel) orthe like. The operation of “crumbling” herein means bringing a gatheredsubstance back to the form or unit before it is gathered, and means anoperation entirely different from stirring to be carried out generallyfor dissolving a substance.

The temperature of the aqueous solvent during mixing the aqueous solventand the galactose-partial degradation product is not particularlylimited, provided that it is at room temperature, but the temperature tobe employed is preferably 18 to 30° C., more preferably 18 to 28° C. Bymixing at 18° C. or higher, it is possible to disperse thegalactose-partial degradation product in the aqueous solvent, whilefurther avoiding occurrence of undissolved lumps. Thereby, it ispossible to further suppress increase in viscosity caused, for example,when the galactose-partial degradation product has been dissolved. Thus,it is possible to suppress deterioration of workability. Further, as aresult of the mixing at 30° C. or lower, the galactose-partialdegradation product can be dispersed in the aqueous solvent under theordinary environment at room temperature without need for specialconditions such as heating, thereby enabling these steps to be performedby a simple operation. The aforementioned mixing may be performed whilethe heating is performed. Thus, it is possible to suppress deteriorationof workability by mixing the galactose-partial degradation product andthe aqueous solvent at 18 to 30° C.

The time for mixing the aqueous solvent with the galactose-partialdegradation product is not particularly limited and may be appropriatelyset when considering that the galactose-partial degradation product hasa very good affinity to the aqueous solvent at the aforementionedtemperature. The mixing time to be employed is, for example, 5 minutesto 1 hour, and preferably 10 minutes to 30 minutes. Setting the mixingtime at 1 hour or less is advantageous in that the operation can befinished earlier and the workability can be improved.

The content of the galactose-partial degradation product in the aqueoussolvent is not particularly limited and may be appropriately set. Forexample, the content may be suitably set according to the desired gelcharacteristics of the gel composition to be obtained. In view of thisaspect, the content of the galactose-partial degradation product in themixture is preferably 0.05 to 20 mass %, more preferably 1 to 10 mass %,still more preferably 3 to 10 mass %, and further preferably 3 to 5 mass%, for example. With the content of the galactose-partial degradationproduct of 0.05 mass % or more in the mixture, it is possible to moresecurely gel the mixture. Further, the galactose-partial degradationproduct content of 3 mass % or more is preferable when considering thata water layer may be not easily formed on the surface of the gel.Meanwhile, with the content of galactose-partial degradation product of20 mass % or less, it is possible to allow a moderate amount of water tobe retained in the gel so that a gel composition capable of exhibitingdesired gel characteristics can be produced. Further, a gel compositioncapable of further exhibiting desired gel characteristics can beproduced by mixing together the respective components of the mixturewithin a shallow (small depth) container (that is, in a state where thedepth of the mixture is made small). When the concentration of thegalactose-partial degradation product is low, water that could notcontribute to gelation may form a layer on the upper side of the gelcomposition and the rest below it may form a gelled layer by heating thelater-described cooled or frozen mixture. In this case, it is alsopossible to obtain the gel layer below the water layer (separated water)as a gel composition by removing the water layer (separated water) onthe upper side. That is, it is possible to produce a gel composition byconcentration of the later-described cooled or frozen mixture. Whenconsidering that the water layer is thus removed depending on theconcentration of the galactose-partial degradation product, theconcentration of the galactose-partial degradation product in theproduced gel composition (when the water layer is removed, the gelcomposition after the removal, and when the water layer does not occur,the gel composition as produced) is preferably 1 to 20 weight %, morepreferably 1 to 10 weight %, and still more preferably 2 to 5 weight %.

The aqueous solvent is not particularly limited provided that it is asolvent containing water; however, water, salt aqueous solution, and thelike can be mentioned, for example. As the salt aqueous solution, sodiumsalt aqueous solution, calcium salt aqueous solution, buffer solution,and the like can be mentioned. As the buffer solution, a phosphatebuffer solution, a citrate buffer solution, and the like of pH 4 to 7can be mentioned.

According to step (1), it is also possible to obtain the gel compositionas a molded article formed into a desired shape by transferring themixture to a mold or the like having a desired shape before cooling orfreezing in step (2).

In step (2), the mixture obtained in step (1) is cooled or frozen. Morespecifically, a hydrated swollen product in which the galactose-partialdegradation product is hydrated and swollen in the aqueous solvent isobtained by cooling or freezing the dispersion liquid obtained in step(1). Examples of the hydrated swollen product include a hydrated swollenproduct in liquid form that has been cooled but not frozen and ahydrated swollen product in solid form that has been frozen. In step(2), the aqueous solvent may include a dissolved product resulting frompartial dissolving of the galactose-partial degradation product.

According to step (2), the galactose-partial degradation productdispersed in the aqueous solvent in step (1) can be hydrated and swollenwith water in the aqueous solvent by cooling or freezing the mixture ofthe aqueous solvent and the galactose-partial degradation product. Sincehydration and swelling can be thus produced, the development ofviscosity can be relatively delayed, and thereby the galactose-partialdegradation product can be dispersed in the aqueous solvent without needfor forcible stirring with a relatively strong force as conventionallyneeded. Thus, the production method is simplified because the need forforcible stirring can be eliminated. In step (2), forcible stirring isnot necessarily eliminated, but when forcible stirring is performed, thehydration and swelling of the galactose-partial degradation product canbe more quickly produced than in the case of skipping the forciblestirring.

In the cooling or the freezing, the degree by which the temperature ofthe mixture is to be lowered is not particularly limited and may beappropriately set, provided that the galactose-partial degradationproduct in the mixture (dispersion liquid) obtained in step (1) can behydrated and swollen. As the degree by which the temperature of themixture is lowered is greater, the galactose-partial degradation producttends to be more easily hydrated and swollen, but on the other hand, thehydration and swelling tends to excessively progress to thereby causethe viscosity to be easily developed. In view of this aspect, it ispreferable to cool or freeze the mixture obtained in step (1) to −25 to10° C., for example. When the upper limit of the range of temperature,to which the temperature of the mixture is lowered, is set at 10° C. orlower, the galactose-partial degradation product is easily hydrated andswollen. The upper limit is more preferably 5° C. or lower, still morepreferably 1° C. or lower when considering that the hydration andswelling of the galactose-partial degradation product can be produced atsuch a temperature. On the other hand, when the lower limit of the rangeof temperature to which the temperature of the mixture is lowered is setat −25° C., excessive progress of hydration and swelling is suppressed,thereby making it hard for the viscosity to develop.

In step (3), the gel composition including the galactose-partialdegradation product can be obtained by heating the mixture cooled orfrozen in step (2), thereby gelling the same. More specifically, in step(3), the gel composition including the galactose-partial degradationproduct is obtained by heating the hydrated swollen product obtained instep (2), thereby gelling the same.

In the heating, the degree by which the temperature of the cooled orfrozen mixture (hydrated swollen product) obtained in step (2) is to beraised is not particularly limited and may be appropriately set,provided that the mixture is raised to a temperature at which themixture can be fully gelled. As the degree by which the temperature ofthe mixture is raised is greater, the gel strength can be increased, buton the other hand, unnecessary heating operation is increased and hencethe workability tends to be deteriorated. In view of this aspect, it ispreferable to raise the temperature of the cooled or frozen mixture to25 to 60° C., for example. The gel strength can be sufficientlyincreased by setting the lower limit of the range of temperature, towhich the temperature of mixture is raised, at 25° C. The lower limit ismore preferably 40° C. or higher when considering that the gel strengthcan be more sufficiently increased. Meanwhile, when the upper limit ofthe range of temperature, to which the temperature of mixture is raised,is 60° C. or lower, unnecessary heating operation can be suppressed andhence the workability is suppressed from being deteriorated. The upperlimit is still more preferably 50° C. or lower from the aspect ofsuppressing unnecessary heating operations.

The gel composition of this embodiment is a gel composition including agalactose-partial degradation product obtained by the production methodof this embodiment. The gel composition of this embodiment preferablyhas heat resistance and water resistance.

As mentioned above, the production method for the gel composition ofthis embodiment includes steps (1) to (3) mentioned below:

step (1) of mixing at room temperature a partial degradation product ofthe galactose moiety of galactoxyloglucan and an aqueous solvent toobtain a mixture;

step (2) of cooling or freezing the mixture obtained in step (1); and

step (3) of gelling the mixture cooled or frozen in step (2) by heatingto obtain a gel composition that includes the galactose-partialdegradation product.

With the production method for the gel composition of this embodiment,in step (1), the partial degradation product of the galactose moiety ofgalactoxyloglucan is mixed with the aqueous solvent at room temperatureso that the galactose-partial degradation product can be dispersed inthe aqueous solvent without occurrence of undissolved lumps in themixture. In step (2), the mixture obtained in step (1) is cooled orfrozen, and thereby the galactose-partial degradation product can behydrated and swollen in the aqueous solvent. At this time, it ispossible to easily bring the galactose-partial degradation product intonot the dissolved state but the hydrated swollen state. Thereby, it ispossible to lower the viscosity of the mixture and allow the mixture tobe a hydrated swollen product having high viscosity by cooling orfreezing the mixture. Further, since the development of viscosity can berelatively delayed, the galactose-partial degradation product can befully dispersed in the aqueous solvent without need for forciblestirring with a relatively strong force as conventionally needed.Moreover, with steps (1) and (2), it is not necessary to cool theaqueous solvent in advance, and therefore time and labor for preparationcan be eliminated. Then, in step (3), the mixture cooled or frozen instep (2) can be gelled by heating to produce a gelled mixture. The gelcomposition obtained this time is suppressed from having non-hydratedproducts such as undissolved lumps, which are caused by thegalactose-partial degradation product, mixed therein. In step (3), whenthe cooled mixture is heated, it is preferable that the mixture bethawed by heating, then forcibly stirred, and then heated, andalternatively, it is preferable that the mixture be heated while beingforcibly stirred after it is thawed by heating. Thus, a more homogeneousgel composition is obtainable by forcibly stirring while heating. Suchforcible stirring is preferable particularly in step (3) for thegalactose-partial degradation product having such a low concentration inwhich an aqueous layer is formed, and the gel composition can be morehomogenized by being subjected to the forcible stirring. Accordingly,the method including steps (1) to (3) enables to easily produce the gelcomposition including the galactose-partial degradation product.

When an attempt is made to disperse a polysaccharide such as a locustbean gum in an aqueous solvent at room temperature, undissolved lumpsmay occur, which causes a lot of time or the necessity for heating toeliminate the undissolved lumps. Therefore, the polysaccharide needs tobe dispersed by, for example, being forcibly stirred or heated afterintroduction into the aqueous solvent. After the dispersion, the mixturemust be gelled by freezing and further thawing. However, if the heatingis continued after the thawing, gel transfers to sol, and hence geldissolves. On the other hand, the galactose-partial degradation productis not solated even if it is continuously heated after cooling, asmentioned above.

The galactose-partial degradation product used for the production methodof this embodiment has reverse thermal gelation characteristics, asmentioned above, and specifically, has characteristics where it isgelled by heating around the body temperature. Thus, in the productionmethod of this embodiment, the mixture (hydrated swollen product at acomparatively low temperature) obtained in step (2) may be applied tothe skin to carry out the gelation in step (3) through the bodytemperature, for example. That is, the gel composition may be preparedwhen needed. The mixture (hydrated swollen product) after cooling orfreezing in step (1) may be allowed to stand still for storage at a lowtemperature of 15° C. or lower until it is used in step (3) as needed.The thus stored mixture may be moved to a mold having a desired shapebefore heating in step (3), and then subjected to step (3) in this stateto thereby obtain a gel composition as a molded article.

In step (1) of the production method for the gel composition of thisembodiment, the galactose-partial degradation product and the aqueoussolvent are preferably mixed together at 18 to 30° C.

With such construction, the galactose-partial degradation product can bedispersed in the aqueous solvent in ordinary room-temperatureenvironments, while further avoiding occurrence of undissolved lumps bymixing together the galactose-partial degradation product and theaqueous solvent at 18 to 30° C. Thus, it is possible to suppressdeterioration of workability.

In step (1) of the production method for the gel composition of thisembodiment, 30 to 55% of a galactose moiety is preferably degraded inthe galactose-partial degradation product.

With such construction, by using the aforementioned galactose-partialdegradation product in which 30 to 55% of the galactose moiety isdegraded, it is possible to produce a gel composition that is notexcessively hard, while allowing it to exhibit sufficient gelationcharacteristics by heating.

In step (2) of the production method for the gel composition of thisembodiment, the mixture obtained in step (1) is preferably cooled orfrozen to −25 to 10° C.

With such construction, by cooling or freezing the mixture to −25 to 10°C., the galactose-partial degradation product is easily hydrated andswollen, and excessive progress of hydration and swelling is suppressed.

In step (1) of the production method for the gel composition of thisembodiment, 0.05 to 20 mass % of the galactose-partial degradationproduct is preferably mixed in the mixture.

With such construction, it is possible to allow the mixture to be surelygelled and allow a moderate amount of water to be retained in the gel,thereby enabling to produce a gel composition capable of exhibitingdesired gel characteristics, when the content of the galactose-partialdegradation product is 0.05 to 20 mass %.

In the production method for the gel composition of this embodiment, theaqueous solvent preferably includes water or salt aqueous solution.

The gel composition of this embodiment includes a partial degradationproduct of the galactose moiety of galactoxyloglucan obtained by theaforementioned production method for the gel composition.

As mentioned above, according to these embodiments, there are provided aproduction method that can relatively easily produce a gel compositionincluding a partial degradation product of the galactose moiety ofgalactoxyloglucan, and a gel composition produced by this productionmethod.

Since the gel composition obtained by the production method of theseembodiments has characteristics where it is produced by being gelled byheating, it is usable as a polymer material in various industries, suchas those for domestic purposes, medical field, biomaterials, cosmeticsand hence usable in various fields. The galactose-partial degradationproduct used in these embodiments is not obtained by chemicalmodification of a natural substance derived galactoxyloglucan, and thusthe obtained gel composition is also harmless to the living body.

The description for the gel composition and the production methodtherefor according to the embodiments was thus made, but the presentinvention is not limited to the aforementioned embodiments, and variousmodifications can be appropriately made within the intended scope of thepresent invention. In the gel composition and the production methodtherefor, additives other than the galactose-partial degradation productand the aqueous solvent may be appropriately added, for example.

EXAMPLES

The present invention will be hereinafter described in detail withreference to examples but the present invention is not limited to thoseexamples.

(Production Example 1) Production of a Partial Degradation Product ofthe Galactose Moiety of Galactoxyloglucan Purification ofβ-galactosidase

A 2.5% aqueous solution of a commercially available β-galactosidasehaving complex enzyme activity “LACTASE Y-AO” [derived from Aspergillusoryzae, manufactured by Yakult Pharmaceutical Industry Co., Ltd.] wassubjected to 0 to 0.6 M NaCl gradient with 0.025 M phosphate buffer (pH7.4) of an ion exchange chromatography [DEAE Toyopeal, manufactured byTosoh Corporation] to obtain eluate at a NaCl concentration of 0.2 to0.4 M. Furthermore, the obtained eluate was subjected to 0 to 0.6 Mammonium sulfate gradient with 0.025 M phosphate buffer (pH 7.4) of ahydrophobic chromatography [Butyl-Toyopeal, manufactured by TosohCorporation] to obtain eluate at an ammonium sulfate concentration of10% or less. 60 mg of the purified enzyme was obtained from 2.5 g of acommercially available crude enzyme by these operations. Cellulaseactivity and IPase (isoprimeverose generation enzyme) activity were notfound in this product.

Production of a Galactose-Partial Degradation Product

Using the purified enzyme β-galactosidase obtained above, an aqueoussolution of 1% substrate galactoxyloglucan [GLYLOID (registeredtrademark), manufactured by DSP GOKYO FOOD & CHEMICAL Co., Ltd.] wasreacted at an enzyme concentration of 2.4×10⁻⁵ mass %, a pH of 5.6, anda temperature of 50° C., and thereafter heated at 100° C. for 20 minutesto stop the reaction. The obtained reaction solution was gelled in about15 hours after the reaction start, and, as a result, a gelledcomposition was obtained. The galactose removal ratio in the obtainedgelled composition was calculated by the method below. 1 mL of asolution with 0.15 mass % of Cellulase Onozuka RS [manufactured byYakult Pharmaceutical Industry Co., Ltd.] (50 mM acetic acid buffersolution, a pH of 4.0) was added to 7 g of an aqueous solution with 1mass % of the gelled composition to react at 50° C. overnight. Anaqueous solution with 1 mass % of galactoxyloglucan was also made toreact in the same manner and an obtained product was employed as acontrol. After the reaction, the enzyme was deactivated by heating thereaction liquid for 30 minutes at 98° C. Then, a sample was subjected toa pretreatment cartridge [IC-SP, manufactured by Tosoh Corporation] anda membrane filter of 0.45 μm cellulose acetate to obtain filtrate. 10 μLof the obtained filtrate was applied to an amino column of HPLC, inwhich acetonitrile:water=60:40 (v/v) was made to flow at 0.6 mL/min, sothat elution areas of oligosaccharides (heptasaccharide (0galactosemoiety), octasaccharide (1 galactose moiety), nonasaccharide (2galactose moieties)) of galactoxyloglucan were detected using arefractive-index meter equipped therein. Then, the amount of galactoseper unit (heptasaccharide) was calculated by an expression (area ofoctasaccharide+(area of nonasaccharide×2)/(area of heptasaccharide+areaof octasaccharide+area of nonasaccharide). When the decreasing ratio ofthe amount of galactose determined on the gel composition from theamount of the galactose calculated from the control galactoxyloglucanwas designated as the galactose removal ratio (%) and calculation wasfurther made, the galactose removal ratio was found to be about 45%.Then, the thus obtained gelled composition was subjected to freezedehydration, or was subjected to sedimentation and filtering subsequentto the addition of alcohol to the gelled composition, followed bydrying, to obtain a galactose-partial degradation product in powderform.

In the following experimental examples, a product produced by heatingafter cooling or freezing the dispersion liquid in which thegalactose-partial degradation product has been dispersed in water atroom temperature was served as Example, and a product produced byheating an aqueous solution (dissolved solution), in which thegalactose-partial degradation product has been dissolved in cold waterwhile being stirred, was served as Comparative Example.

Experimental Example 1 (1) Production of Gel Compositions by Freezingand Heating

The galactose-partial degradation product produced in Production Example1 was added into 200 mL tall beakers, followed by adding water at roomtemperature (25° C.) thereto, to disperse by lightly crumbling withspatula (spatel). Thus, 100 g of the dispersion liquids were preparedwith the galactose-partial degradation product contents of 0.05 mass %(Example 1), 0.1 mass % (Example 2), 1 mass % (Example 3), 3 mass %(Example 4), 5 mass % (Example 5), 10 mass % (Example 6), 15 mass %(Example 7), and 20 mass % (Example 8), respectively. After thepreparation of the dispersion liquids, each 20 g of the prepareddispersion liquid was dispensed into each of four screw cap glass vials[No. 35; content: 30 mL, manufactured by Maruemu Corporation], and therest was dispensed into the fifth screw cap glass vial. The amount ofeach of the dispersion liquids remained and adhered to the tall beakerafter the dispensing (C) was calculated by measuring the mass of thetall beaker after the dispensing (A), and deducting the mass of the tallbeaker itself (B) (tare), which was measured in advance, from the mass(A) (C=A-B). The ratio of the amount of the dispersion liquid (C) basedon 100 g of the dispersion liquid before dispensing was calculated bythe expression: (C/100)×100. This calculation result was served as thesample loss rate (%) of the dispersion liquid. Further, each of thedispensed dispersion liquids was allowed to stand still for 2 hours in afreezer [manufactured by HOSHIZAKI ELECTRIC CO., LTD., model: HRF-180XF]set at −20° C. to lower its temperature to −20° C., then left for 2hours in this state, and then thawed at room temperature. Thereafter,each of the dispersion liquids was allowed to stand still in a warm bathto have its temperature raised to 40° C., and then left for 2 hours inthis state to thereby produce a gel composition.

(2) Production of Gel Compositions by Stirring and Dissolving in ColdWater, and Heating

The galactose-partial degradation product produced in Production Example1 was dispersed and dissolved in water added into a 200 mL tall beaker,while being forcibly stirred under ice cooling by a stirrer [productname: Three-One Motor] with a propeller stirring blade attached thereto.Thus, 100 g of aqueous solutions were prepared with thegalactose-partial degradation product contents of 0.05 mass %(Comparative Example 1), 0.1 mass % (Comparative Example 2), 1 mass %(Comparative Example 3), 3 mass % (Comparative Example 4), 5 mass %(Comparative Example 5), 10 mass % (Comparative Example 6), 15 mass %(Comparative Example 7), and 20 mass % (Comparative Example 8),respectively. The amount of each of the aqueous solutions remained andadhered to the stirrer (E) was calculated by measuring the mass of thetall beaker containing the aqueous solution (D) after the stirrer wastaken out from the aqueous solution, and deducting the mass of the tallbeaker itself (B) (tare), which was measured in advance, from the mass(D). Subsequently, each 20 g of the aqueous solution remained in thetall beaker after the stirrer was taken out was dispensed into each offour screw cap glass vials, and the rest was dispensed into the fifthscrew cap glass vial. The amount of each of the aqueous solutionsremained and adhered to the tall beaker after the dispensing (C′) wascalculated by deducting the mass of the tall beaker itself (B) (tare),which was measured in advance, from the mass of the tall beaker afterthe dispensing (A). The ratio of the total of the amount of the aqueoussolution removed as a result of adhering to the stirrer (E) and theamount of the aqueous solution remained and adhered to the tall beakerafter the dispensing (C′) based on the original amount of 100 g wascalculated by the expression: ((E+C′)/100)×100). This calculation resultwas served as the sample loss rate (%) of the aqueous solution. Further,each of the dispensed aqueous solutions was allowed to stand still for 2hours in a freezer [manufactured by HOSHIZAKI ELECTRIC CO., LTD., model:HRF-180XF] set at −20° C. to lower its temperature to −20° C., then leftfor 2 hours in this state, and then thawed at room temperature.Thereafter, each of the aqueous solutions was allowed to stand still ina warm bath to have its temperature raised to 40° C., and then left for2 hours in this state to thereby produce a gel composition.

(3) Evaluation

Evaluations mentioned below were made. The results are shown in Table 1.

Gelled State (Gel)

The gelled states of the gel compositions dispensed in the screw capglass vials were visually checked. Evaluation was made, upon inclinationof the screw cap glass vial by 90 degrees, by representing as follows:“o” when deformation of the gel was not visually observed; “∘” when thegel was not collapsed while deformation of the gel was observed; “Δ”when the gel was collapsed; and “x” when the gel was not formed. Theresults are shown in Table 1.

Entrainment of Air Bubbles in Gel Compositions (Bubble Entrainment inGel)

In the dispensed gel compositions, evaluation was made by representingas follows: “⊚” when bubbles in the gel were not visually observed or avery small number of bubbles were visually observed; “o” when a smallnumber of bubbles were visually observed; “Δ” when a large number ofbubbles were visually observed; and “x” when a very large number ofbubbles were visually observed. The results are shown in Table 1.

Easiness of Filling (Decantation)

Evaluation was made upon filling the screw cap glass vial with adispersion liquid or a stirred and dissolved solution by representing asfollows: “∘” filling could be made by decantation; and “x” fillingcouldn't be made by decantation. The dispersion liquid or the stirredand dissolved solution which could not be decanted were filled using aspatel or the like. The results are shown in Table 1.

Presence of Water Separation on Gel

Water on each of the gel compositions evaluated as “⊚” and “∘” in theaforementioned evaluation for the gelled state was transferred from thescrew cap glass vial to the plastic cup whose mass was measured inadvance to measure the mass thereof. The mass of water transferred tothe plastic cup was calculated by deducting the mass of the plastic cup(tare) from the obtained total mass. Further, water remained and adheredto the inner wall of the screw cap glass vial was wiped off with theKimwipes [product name: Wiper S-200; manufactured by Nippon Paper CreciaCo., Ltd.] whose mass was measured in advance to measure the massthereof. The mass of the absorbed water was measured by deducting themass of Kimwipes (tare) from the obtained mass. Then, the total of themass of water transferred to the plastic cup and the mass of waterabsorbed by Kimwipes was calculated as the amount of separated water F(g), and the ratio (%) of the amount of separated water F based on themass (20 g) of the dispersion liquid or the aqueous solution dispensedin the screw cap glass vial was calculated as the water separation ratio(%). Further, the mass of the gel composition was calculated bydeducting the amount of the separated water F (g) from the mass of thedispensed dispersion liquid or aqueous solution (20 g) (mass G=20−F).The concentration of the galactose-partial degradation product of thisgel composition was calculated, based on the mass (20 g) of thedispersion liquid or the aqueous solution containing thegalactose-partial degradation product with the concentration H beforeremoving the separated water, by the expression: (20/(20−F)×H). Theobtained value was served as the concentration of the produced gel (mass%). Further, the concentration rate (magnification) was calculated bydividing the obtained concentration of the produced gel by theconcentration I (mass %) of the dispersion liquid or the aqueoussolution before removing the separated water (concentrationrate=(concentration of the produced gel)/I). The results are shown inTable 1. The amount of separated water in the gel composition evaluatedas “Δ” in the above evaluation on the gelled state could not be measuredbecause the content collapsed when the screw cup glass vial containingit was tilted. Since the water separation was not found in the gelcomposition (Examples 5 to 8, Comparative Examples 5 to 8), in which theconcentration of the galactose-partial degradation product was 5 mass %or more, the concentration after dispensing the produced gel compositionwas the same as that of the dispersion liquid or the aqueous solutionbefore removing the separated water. That is, the concentration rate was1 time.

As shown in Table 1, it was found that the gel composition obtained fromthe dispersion liquids including 0.05 to 20 mass % of thegalactose-partial degradation product based on the total mass of thecomposition (Examples 1 to 8) exhibits good gel formation. Whencomparing the composition obtained from the aqueous solutions (stirredand dissolved solutions) containing less than 1 mass % of thegalactose-partial degradation product (Comparative Examples 1 and 2)with the composition obtained from the dispersion liquids with the sameconcentration (Examples 1 and 2), water separation did not occur in theaqueous solution (Comparative Examples). It was found from this that thegalactose-partial degradation product was not concentrated in theaqueous solution (Comparative Examples), and thus the gel formation wasnot confirmed. On the other hand, a water layer was separated on theupper side of the dispersion liquid (Examples), and thereby thegalactose-partial degradation product was concentrated therebelow, whichresulted in good gel formation. When comparing the composition obtainedfrom the aqueous solutions (stirred and dissolved solutions) containing1 mass % of the galactose-partial degradation product (ComparativeExample 3) with the composition obtained from the dispersion liquidswith the same concentration (Example 3), water separation did not occurin the aqueous solution (Comparative Examples). It was found from thisthat the galactose-partial degradation product was not sufficientlyconcentrated in the aqueous solutions (Comparative Example), and thusonly a weak gel having a low strength was produced. On the other hand, awater layer was separated on the upper side of the dispersion liquid(Example), and thereby the galactose-partial degradation product wasconcentrated therebelow, which resulted in producing a good gel having ahigh strength.

As to the bubble entrainment in the gel, it was found that thecompositions (Examples 3 to 5) obtained from the dispersion liquidsincluding 0.05 to 5 mass % of the galactose-partial degradation producttherewith had smaller bubbles entrained therein and better appearancethan the gels obtained from the aqueous solutions with the sameconcentration (stirred and dissolved solutions, Comparative Examples 3to 5).

The dispersion liquid (Examples) could be filled in the screw cap vialby decantation until it reaches 10 mass %, while the aqueous solution(Comparative Examples) could not be filled therein any more bydecantation when it reaches 5 mass % or more, since the aqueous solutionhad excessively high viscosity.

The total sample loss rate (loss, sample loss rate due to the adhesionto the container) when having filled the dispersion liquid was muchsmaller than the total sample loss rate (loss, sample loss rate due tothe adhesion to the container and the stirrer) when having filled theaqueous solution.

Even if water separation occurs on the upper side of the gel in thedispersion liquid, such water separation can be suppressed or adjustedusing a shallow container enabling a small depth of the dispersionliquid, when heating. Specifically, it is possible to adjust theconcentration of the produced gel of the gel composition not only bychanging the original amount of the galactose-partial degradationproduct to be added (concentration) but also by, for example, changingthe depth of the dispersion liquid.

Compositions (Comparative Examples 9 and 10) were produced in the samemanner as the aforementioned Examples using galactoxyloglucan[manufactured by DSP GOKYO FOOD & CHEMICAL Co., Ltd., GLYLOID(registered trademark)] in which a galactose moiety is not removed, theobtained dispersion liquid became viscous body containing large amountsof undissolved lumps and was not gelled even by heating.

TABLE 1 Amount added Cooling Bubble Sample Presence or absence of (mass%) temperature (° C.) Gelled state entrainment in gel loss rate (%)Decantation Water separation on gel Ex. 1 0.05 −20 Δ ⊚ 0.1 ◯ presenceCom. Ex. 1 0.05 — X — 0.02 ◯ — Ex. 2 0.1 −20 ⊚ ⊚ 0.1 ◯ presence Com. Ex.2 0.1 — X — 0.1 ◯ — Ex. 3 1 −20 ⊚ ⊚ 0.3 ◯ presence Com. Ex. 3 1 — Δ Δ2.7 ◯ absence Ex. 4 3 −20 ⊚ ⊚ 0.6 ◯ presence Com. Ex. 4 3 — ⊚ X 7.4 ◯absence Ex. 5 5 −20 ⊚ ⊚ 1.1 ◯ absence Com. Ex. 5 5 — ⊚ X 17.1 X absenceEx. 6 10 −20 ⊚ ◯ 3.7 ◯ absence Com. Ex. 6 10 — ⊚ X 8.9 X absence Ex. 715 −20 ⊚ Δ 1.6 X absence Com. Ex. 7 15 — ⊚ X 6.8 X absence Ex. 8 20 −20⊚ Δ 0.5 X absence Com. Ex. 8 20 — ⊚ X 2.8 X absence Com. Ex. 9 3 −20 X —— — — Com. Ex. 10 5 −20 X — — — — Amount of Amount of Concentration ofproduced Concentration rate separated water (g) separated water (%) gel(mass %) (magnification) Ex. 1 unmeasurable — — — Com. Ex. 1 — — — — Ex.2 18.4 92 1.3 13 Com. Ex. 2 — — — — Ex. 3 11.5 57 2.4 2.4 Com. Ex. 3 0 01 1 Ex. 4 3.3 16 3.6 1.2 Com. Ex. 4 0 0 3 1 Ex. 5 0 0 5 1 Com. Ex. 5 0 05 1 Ex. 6 0 0 10 1 Com. Ex. 6 0 0 10 1 Ex. 7 0 0 15 1 Com. Ex. 7 0 0 151 Ex. 8 0 0 20 1 Com. Ex. 8 0 0 20 1 Com. Ex. 9 — — — — Com. Ex. 10 — —— —

(Experimental Example 2) Cooling Temperature and Gel Formation ofDispersion Liquid of Galactose-Partial Degradation Product

0.6 g (3 mass %) and 1.0 g (5 mass %) of the galactose-partialdegradation product produced in Production Example 1 were added intoscrew cap glass vials, followed by adding water at room temperaturethereto, to obtain a total amount of 20 g of each of dispersion liquidsof the galactose-partial degradation product. Each of the dispersionliquids was cooled at 12° C. (Examples 9 and 10), 11° C. (Examples 11and 12), 10° C. (Examples 13 and 14), 8° C. (Examples 15 and 16), 6° C.(Examples 17 and 18), 4° C. (Examples 19 and 20), 3° C. (Examples 21 and22), 2° C. (Examples 23 and 24), 1° C. (Examples 25 and 26), 0° C.(Examples 27 and 28), −5° C. (Examples 29 and 30), −10° C. (Examples 31and 32), −15° C. (Examples 33 and 34), and −20° C. (Examples 35 and 36)using a thermostatic device [manufactured by ESPEC CORP., model type:PR-2KP], and left in this state for 2 hours to produce a hydratedswollen solution (dispersion liquid). Each sample after cooling waschecked whether the dispersion liquid was frozen or not by visualobservation and touching with spatel. The frozen dispersion liquid wasleft standing at room temperature to be thawed. The dispensedcomposition was raised to a temperature of 40° C. after the thawing, andleft in this state for 2 hours, and thereafter the degree of gelation,the water separation on the upper side of the gel, and the bubbleentrainment in the gel were observed by the aforementioned method. Theresults are shown in Table 2 and Table 3.

As shown in Tables 2 and 3, when the dispersion liquid was cooled at atemperature of 12° C. (Examples 9 and 10), gelation was not confirmed inboth of the samples of 3 mass % and 5 mass %. When cooled at 11° C.(Examples 11 and 12), gelation was confirmed in the sample of 5 mass %.When cooled or frozen at 10° C. or lower and −20° C. or higher (Examples13 to 36), gelation was confirmed in any samples of 3 mass % and 5 mass%. When cooling or freezing at 10° C. or less and −20° C. or more(Examples 13 to 36), gelation was confirmed in both of the samples of 3mass % and 5 mass %. When cooled or frozen at 10° C. or lower and −20°C. or higher, water separation was observed on the upper side of thesample of 3 mass % after heating. Further, it was found that whether thedispersion liquid was frozen or not does not influence on the gelationperformance. The amount of separated water observed on the upper side ofthe gel was constant regardless of the cooling temperature.

TABLE 2 Additive Cooling amount temperature Bubble (mass %) (° C.)Freezing Gel entrainment in gel Ex. 9 3 12 Not frozen X — Ex. 10 5 12Not frozen X — Ex. 11 3 11 Not frozen X — Ex. 12 5 11 Not frozen Δ — Ex.13 3 10 Not frozen Δ ⊚ Ex. 14 5 10 Not frozen Δ ⊚ Ex. 15 3 8 Not frozenΔ ⊚ Ex. 16 5 8 Not frozen ◯ ⊚ Ex. 17 3 6 Not frozen ◯ ⊚ Ex. 18 5 6 Notfrozen ⊚ ⊚ Ex. 19 3 4 Not frozen ⊚ ⊚ Ex. 20 5 4 Not frozen ⊚ ⊚ Ex. 21 33 Not frozen ⊚ ⊚ Ex. 22 5 3 Not frozen ⊚ ⊚

TABLE 3 Additive Cooling Bubble amount temperature Whether entrainment(mass %) (° C.) Frozen or not Gel in gel Ex. 23 3 2 Not frozen ⊚ ⊚ Ex.24 5 2 Not frozen ⊚ ⊚ Ex. 25 3 1 Not frozen ⊚ ⊚ Ex. 26 5 1 Not frozen ⊚⊚ Ex. 27 3 0 Not frozen ⊚ ⊚ Ex. 28 5 0 Not frozen ⊚ ⊚ Ex. 29 3 −5 Notfrozen ⊚ ⊚ Ex. 30 5 −5 Not frozen ⊚ ⊚ Ex. 31 3 −10 Partly frozen ⊚ ⊚ Ex.32 5 −10 Not frozen ⊚ ⊚ Ex. 33 3 −15 Frozen ⊚ ⊚ Ex. 34 5 −15 Frozen ⊚ ⊚Ex. 35 3 −20 Frozen ⊚ ⊚ Ex. 36 5 −20 Frozen ⊚ ⊚

(Experimental Example 3) Heat Resistance of Gel

1.5 g (3 mass %) and 2.5 g (5 mass %) of the galactose-partialdegradation product produced in Production Example 1 were added intosnap cap glass vials [No. 50; content: 60 mL, manufactured by MaruemuCorporation], followed by adding water at room temperature thereto, toobtain a total amount of 50 g of each of dispersion liquids of thegalactose-partial degradation product. Each of the dispersion liquidswas allowed to stand still for 2 hours in a freezer [manufactured byHOSHIZAKI ELECTRIC CO., LTD., model: HRF-180XF] set at −20° C. to haveits temperature lowered to −20° C., then left for 2 hours in this state,and then thawed at room temperature, allowed to have the temperatureraised to 40° C. in a warm bath, and then left for 2 hours in this stateto thereby produce a composition. Thereafter, the snap cap glass vialswere covered from above with aluminum foil, placed on a stainless tray,and allowed to stand still for 1 hour in the oven [model type:WFO-450ND; manufactured by Tokyo Rikakikai Co., Ltd.] set at 110° C.After the standing still, the vials were taken out and tilted by 90degrees. Visual observation for the strength of the gel revealed thatnone of the gels collapsed. On the other hand, water was added into snapcap glass vials, while being forcibly stirred under ice cooling by astirrer [product name: Three-One Motor] with a propeller stirring bladeattached thereto, and 1.5 g (3 mass %) and 2.5 g (5 mass %) of thegalactose-partial degradation product produced in Production Example 1were added thereto to be dispersed or dissolved, to obtain a totalamount of 50 g of each of aqueous solutions of the galactose-partialdegradation product. Each of the aqueous solution was allowed to haveits temperature lowered to −20° C., and then allowed to have itstemperature raised to 40° C., and left in this state, to thereby producea gel composition in the same manner as mentioned above. Thereafter,visual observation for the strength of the gel was performed in the samemanner as the above, which revealed that when this dispersion liquid washeated, expansion of bubbles are caused, which resulted in largedeformation in the gel and hence caused the gel to have its shapecollapsed (broken into pieces separated from each other), because theaqueous solution included a considerable number of bubbles.

(Experimental Example 4) Water Resistance of Gel

1.0 g (5 mass %) of the galactose-partial degradation product producedin Production Example 1 was added into a plastic cup [EI-90, productname: PROMAX, content: 90 mL, manufactured by ASAHIKASEI PAXCORPORATION], followed by adding water at room temperature thereto, toobtain a total amount of 20 g of a dispersion liquid of thegalactose-partial degradation product. The dispersion liquid was allowedto stand still for 2 hours in a freezer [manufactured by HOSHIZAKIELECTRIC CO., LTD., model: HRF-180XF] set at −20° C. to have itstemperature lowered to −20° C., then left for 2 hours in this state,then thawed at room temperature, then heated in a warm bath to have itstemperature raised to 40° C., and left for 2 hours in this state.Thereby, the composition was produced. Thereafter, three gelcompositions (gel compositions produced in the same manner using threeplastic cups) were taken out from the plastic cups and introduced into a500 mL glass beaker with about 300 mL of water contained therein,followed by further adding water thereto to have a total amount of about400 mL. On the other hand, three gel compositions (gel compositionsproduced in the same manner using three plastic cups) were taken outfrom the plastic cups, placed on stainless trays, and covered with wrapsto be served as controls. Gels in water and gels on the stainless trayswere allowed to stand still in an incubator set at a temperature of 25°C. for 24 hours. After the standing still for 24 hours, the gels weretaken out, visual observation was performed on the shape of the gel,which revealed that the gels in water did not collapse.

(Experimental Example 5) Stability of Gel

1.0 g and 2.0 g of the galactose-partial degradation product were addedinto glass vials, followed by adding 0.6 g of HYDROLITE-5 [manufacturedby Symrise AG] as preservative thereto, and then adding water at roomtemperature thereto, to prepare a total amount of 20 g of each ofdispersion liquids respectively including 5 mass % and 10 mass % of thegalactose-partial degradation product. Each of the dispersion liquidswas allowed to have its temperature lowered and raised in the samemanner as the above to produce a composition. The obtained compositionswere left for 3 months at temperatures of 4° C., 25° C., and 40° C. toobserve water separation. The results are shown in Table 4. Theevaluation on whether water was separated or not was made according tothe following evaluation criteria.

Separated: Partial water separation can be observed.

Not separated: Almost no water separation can be observed.

As shown in Table 4, it was revealed that water separation did not occurwhen stored at the temperature of 4° C. and 25° C. until the lapse of 90days in any compositions obtained using the dispersion liquids with 5mass % and 10 mass % of the galactose-partial degradation product. Itwas also revealed that, when stored at 40° C., significant waterseparation did not occur until the lapse of 14 days in the dispersionliquid with 10 mass % of the galactose-partial degradation product, anduntil the lapse of 60 days in the dispersion liquid with 5 mass % of thegalactose-partial degradation product.

TABLE 4 Presence or absence of water Storage period Amount addedseparation in each storage temperature (day) (%) 4° C. 25° C. 40° C. 7 5absence absence absence 10 absence absence absence 14 5 absence absenceabsence 10 absence absence absence 30 5 absence absence absence 10absence absence presence 60 5 absence absence absence 10 absence absencepresence 90 5 absence absence presence 10 absence absence presence

(Test Example 1) Viscosity Change of Galactoxyloglucan andGalactose-Partial Degradation Product

Water at 25° C. was added to galactoxyloglucan [manufactured by DSPGOKYO FOOD & CHEMICAL Co., Ltd., GLYLOID (registered trademark)], inwhich a galactose moiety is not removed, and the galactose-partialdegradation product to allow them to disperse in water, to therebyobtain dispersion liquids including 1.5 mass % and 5 mass % of therespective components. Thereafter, increase in viscosity of each of thedispersion liquids was measured by a rapid visco analyser [model: RVA-4;manufactured by Newport Scientific Inc.] for 60 minutes. The increase inviscosity with time represents that dissolution is in progress. As shownin the FIGURE, the viscosity greatly increased immediately after thedispersion of galactoxyloglucan, while the viscosity did not change inthe dispersion of the galactose-partial degradation product. It wasfound from the above results that the dispersion liquid including thegalactose-partial degradation product is easier to handle than thedispersion liquid including galactoxyloglucan, in which a galactosemoiety is not removed, since the galactose-partial degradation producthardly progresses from the hydrated and swollen state to the dissolutionstate after dispersion and hence does not increase in viscosity.

The invention claimed is:
 1. A hydrated swollen product comprising 5 to20 mass % of a partial degradation product of the galactose moiety ofgalactoxyloglucan in an aqueous solvent, wherein the partial degradationproduct of the galactose moiety of galactoxyloglucan in powder form isundissolved in the aqueous solvent, while absorbing the aqueous solventtherein and being suspended in the aqueous solvent.
 2. The hydratedswollen product according to claim 1, which is used for preparing a gelcomposition.
 3. The hydrated swollen product according to claim 1, whichis cooled to 15° C. or lower.
 4. A production method for a gelcomposition, comprising steps (1) to (3) mentioned below: step (1) ofmixing at 18 to 30° C. a partial degradation product of the galactosemoiety of galactoxyloglucan in powder form and an aqueous solvent toobtain a mixture; step (2) of cooling or freezing the mixture obtainedin step (1) to produce the hydrated swollen product according to claim1; and step (3) of gelling the hydrated swollen product obtained in step(2) by heating to obtain a gel composition that comprises thegalactose-partial degradation product.
 5. The production method for thegel composition according to claim 4, wherein, in step (2), the mixtureobtained in step (1) is cooled or frozen to −25 to 10° C.
 6. Theproduction method for the gel composition according to claim 4, whereinthe aqueous solvent is water or salt aqueous solution.